Manufacture of glycerin nitrates.



UNITED: STATES PATENT on-From ANTON MIKOLAJ-CZAK, or KASTR-OP, GERMANY. MANUFACTURE OF GLYCERIN NITRATES.

Specification of Letters Patent.

Patented Sept. 11, 1906.

Application filed January 5, 1906. Serial No. 239,732.

in my application, Serial No. 203,762, filed April 18, 1904, on which United States Patent No. 798,436 was granted to me, and in my c'opcnding United States application, Serial solving medium.

No. 229,961, filed October 25, 1904, I have described a process of manufacturing explosives in which dinitroglycerin'is used as a The present invention relates more par- 20. .ticularly to a process whereby (linitroglycerin is manufactured in conjunction with trinitroglycerin in such proportions as to produce a mixture of 'di and tri nitroglycerin in Which the former rcprescntsat least three percent. of the nitroglycerins. Thereb a noduct is obtained which compared with ot er nitroglyocrins shows certain advantages of essential importance, due to the presence of dinitroglyccrin, the characteristic features of which have been more fully set .forth in my above a plication, Serial No. 203,762, (United States atent, No..798,436.)

I found that with the aid of dinitroglycerin gunpowders and explosives gen- .(nially' can be manufactured which possess a high degree of stability, retain their plastic character and form, even during the coldest winters, and are in no wise inferior in force .andeffect to nitroglycerin explosives at present in generaluse, while by proper choice of, the components they can be so manufactured as to afford safety against the ignition of firc-dampand coal-dust in mines. As the percentage of dinitroglycerin increases the tendency to freeze (characteristic of trinitro glycerin) diminishes, so that'it is of great advantage in the manufacture of glycerin nitrateif the product contains a high percentage of dinitroglycerin.

, glycerin as at present conducted great importance is attached to the production of as pure a trinitroglycerin as possible. For this rear,

Thus, for example, a 'mtrate containing some twenty parts tri son it is customary under the term nitro-- glycerin to mean trinitroglycerin. Any dinitroglycerin which may have formed unintentionally in the nitroglycerin iselilnina'ted from the final product, inthe purifying (washing) process. As manufacturing materials it is customary to employ glycerin and a so-called nitrating mixture, consisting,

'for instance, of nitric acid and sulfuric acid (with or Without the addition of other dehydrating substances) or of saltpeter and sulfuric acid. a

The object of the process forming the subj cot of the present invention in contradistinction to not rich in initroglycerin. The new process consists in separating the oil from the charge as far as possible in order to avoid loss of dinitroglycerin, and this is done by adding subsequent. to the nitration of the char e sub-' prior methods is to obtain a prodstances which wholly or partly neutra ize the superfluous acid. uch agents are, for example, caustic alka'lisand carbonates of the alkalies and alkaline earths.' L

In order to promote the production of di-. nitroglycerin inthe charge, the proportions of glycerin and of nitric and sulfuric acids (which according to present practice are generally about one to three to five) may advantageously be altered, less sulfuric acid and, if desired, more glycerin being employed. In order that the dinitroglycerin formed in the charge may be the easier obtained, the quan tity of water employed for the washin g operation should be very small, while, on the other hand, thecharge after each washing is al lowed to stand for a considerable time in order that it may clarify.

As an example of manufacturing dinitroglycerin in mixture withtrinitroglycerin directly I may cite the following: To sixty parts, by weight, of dynamite-glycerin sixtyfouiabarts, by weight, of sulfuric acid. (1.83

specific gravity) mixed with 127.5 parts, by

weight, of nitric acid (1.50 specific gravity) are slowly added, and the mixture is stirred and kept cool at a temperature, by preference, below 26 Celsius. lowed to stand for half an hour, while the 7 temperature is reduced, preferably, to 12 Celsius', whereupon the nitrated glycerin or oil can be separated from the acids. The said Themixture is then al-' oil when sufiicientlypurified contains twentysix per cent. trinitroglycerin and seventyfour per cent. dlnitroglycerin, or the process may be carried out as follows: To one hundred arts, by weight, of concentrated glycerin 0 1 .2 61- to 1.262 specific gravity a mixture of one hundred and eighty parts, by weight, of sulfuric acid of 1.795 specific gravity, and two hundred and fifty parts, by weight of nitric acid of 1.5 specific gravity is slowly added, the whole bein continually stirred and cooled meanwhile. gince the cold syrupy glycerin is diflicult to agitate, it is advisable to first dissolve the one hundred parts of glycerin, while constantly stirring and cool ing,in, say, ninety parts of nitric acid of 1.5 specific gravity. To prevent oxidation, the temperature of the mixture should be kept between and centigrade. To this solution a mixture of one hundred and sixty parts, by weight, of concentrated nitric acid and one hundred and eighty parts, by Weight, of sulfuric acid of 1.795 specific gravity (64 Baum) is slowly added during continuous stirring, and by cooling the term perature is kept, if possible, below centigrade, or the one hundred parts, by weight, of glycerin may be first dissolved in the two hundred and fifty parts, by weight, of nitric acid, the mixture, if desired, allowed to stand for a time in order to complete nitration and the sulfuric acid then added. The charge is then diluted with cold water, and for the purpose of precipitating or ehminating therefrom the oil dissolved in the acid liquid the alkali-for example, carbonate of limeor a solution of soda (about Baum) is added to it until the charge shows alkaline reaction. The oil may be separated from the aqueous liquid in the ordinary manner in a separatory funnel or other suitable a paratus, whereupon the oil is purified, as above set out.

The roduct thus obtained is one which, as will lie seen, still contains a large amount oftrinitroglycerin. The percentage of dinitroglycerin in the final product will, however, be the higher the snialler the quantity of sulfuric acid in proportion to nitric acid employed. Thus by suitably proportioning the nitrifying mixture with regard to the quantity of glycerin the percentage of dinitroglycerin and trinitroglycerin in the final product can be controlled, the degree of concentration of the reagentsythe duration ofthe nitrating operation, and the temperature also exerting a certain influence, as is well known to those skilled in the art.

What I claim as my invention, and desire to secure by Letters Patent, is-

1. The process of manufacturing a mixture of glycerin nitrates containing dinitroi glycerin and trinitroglycerin, which consists in reacting on glycerin with nitric acid in the presence of a dehydrating agent, in such proportions as are adapted to make dinitroglycerin, maintaining a low temperature until dinitroglycerin is formed in the acid solution, separating the dinitroglycerin by means of a neutralizing agent and removing the separated dinitrogylcerin with the trinitroglycerin.

2. Theprocess of manufacturing a mixture of glycerin nitrates containing dinitroglycerin and trinitroglycerin, which consists in reacting on glycerin with nitric acid, in the presence of a dehydrating agent, in such pro portions as are adapted to makedinitro lycerin, separating the dinitroglycerin he d in solution and removing the separate d dinitroglycerin with the trinitroglycerin.

3. The process of manufacturing a mixture of glycerin nitrates containing any desired proportion of jdinitroglycerin and trinitroglycerin, which consists in reacting upon glycerin with nitric acid in the presence of a dehydrating agent, the relative proportions and concentration of the dehydrating agent, the nitric acid and the glycerin bein such as to produce the desired proportions o dinitroglycerin and trinitroglycerin as described, and separating the dimtroglycerin from the solution in which it is held.

4. The process of manufacturing a mixture of glycerin nitrates containing any desired proportions of dinitroglycerin and trinitro glycerin, which consists in reacting on glycsun with nitric acid and a dehydrating agent,

the relative proportions and concentration of the dehydrating agent, the nitric acid and the glycerin being sue as to produce the desired proportions ofdinitroglycerin and trinitroglycerin as. described, and separating the dinitroglycerin from the acid solution by neutralizing the excess of acid.

glycerin compound containing dinitroglycarm and trimtro lycerin, the former re resenting at least t a; per cent. of the nitroglycerms.

name to this specification in the presence of two subscribing witnesses. Y A

ANTON MIKOLAJOZAK.

Witnesses:

Bananas]: Galirz, K

CARL GARZ.

In testimony whereof I have signed my I V 5. As a newarticle of manufacture a nitro- 

